WO1997006687A1 - Active substance combinations comprising pyrethroids and insect-development inhibitors - Google Patents

Active substance combinations comprising pyrethroids and insect-development inhibitors Download PDF

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Publication number
WO1997006687A1
WO1997006687A1 PCT/EP1996/003455 EP9603455W WO9706687A1 WO 1997006687 A1 WO1997006687 A1 WO 1997006687A1 EP 9603455 W EP9603455 W EP 9603455W WO 9706687 A1 WO9706687 A1 WO 9706687A1
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Prior art keywords
active substance
spray
spp
combinations according
contain
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Application number
PCT/EP1996/003455
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German (de)
French (fr)
Inventor
Klaus Mrusek
Manfred-Heinrich Schütte
Original Assignee
Bayer Aktiengesellschaft
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Priority claimed from DE19605773A external-priority patent/DE19605773A1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to MX9801242A priority Critical patent/MX9801242A/en
Priority to JP9508896A priority patent/JPH11511152A/en
Priority to BR9610228-4A priority patent/BR9610228A/en
Priority to EP96927686A priority patent/EP0845944B2/en
Priority to DE59606147T priority patent/DE59606147D1/en
Priority to AU67424/96A priority patent/AU706903B2/en
Priority to US09/011,451 priority patent/US6270784B1/en
Publication of WO1997006687A1 publication Critical patent/WO1997006687A1/en
Priority to GR20010400209T priority patent/GR3035382T3/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to new active substance combinations of pyrethroids with insect development inhibitors, in order to achieve a long-term action against animal pests, in particular insects and arachnids, with high effectiveness, less environmentally harmful properties and a toxicologically favorable control concept.
  • Insecticidal classes of compounds that do not show cross-resistance are usually combined. In this way, formulations are obtained which also have a good action against resistant species (W. Behrenz, K. Naumann, Plant Protection News Bayer, 35, 309 (1982)).
  • insect development inhibitors have recently become known. These are so-called juvenile hormones and chitin synthesis inhibitors from the benzoyl urea class, which specifically influence the development cycle of insects by preventing the conversion of the individual larval stages into the next higher development stages.
  • This principle of action is specific to insects and does not occur in warm-blooded animals. In addition to an extremely effective prevention of the development of new generations of insects, this also results in the complete absence of side effects on the warm-blooded animals, as a result of which a toxicologically favorable control concept is achieved. However, such development inhibitors have no effect on adult stages of insects, so that the effect only occurs after a waiting period of up to two weeks.
  • Pyrethrum, allethrin or transfluthrin are preferred as pyrethroids, insecticides and chitin synthesis inhibitors, such as e.g. Lufenuron,
  • RH 5849 (2-benzoyl-l- (l, l-dimethylethylbenzoic acid hydrazide), chlorofluazuron, difiubenzuron, N - [[[3,5-dichloro-4- (4-chlorophenoxy) phenyl] amino] carbonyl], 2,6- difluorobenzamide; flufenoxuron; flucycloxuron; penfluron; teflubenzuron; hexaflumuron; tebufenozide; 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide; sodium 1,4-bis- (2-ethylhexyl) sulfobutanedioate; novaluron, 2-
  • Particularly preferred combinations of active ingredients consist of transfluthrin, allethrin or pyrethrum on the one hand and fenoxycarb, pyriproxyfen, triflumuron, flufenoxuron and / or methoprene on the other.
  • Combinations of active substances consisting of transfluthrin of the formula (I) and triflumuron of the formula (II) and / or are very particularly preferred
  • Transfluthrin of formula (I) and flufenoxuron (III) surprisingly have a synergistic effect.
  • the active compound combinations according to the invention are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. To the animal mentioned above, insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. To the animal mentioned above, insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. To the animal mentioned above, insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the
  • Pests include:
  • Isopoda for example Oniscus asellus, Armadillidium vulgare, Por ⁇ cellio scaber.
  • Diplopoda for example, Blaniulus guttulatus.
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Aleurodes brassicae Bemisia tabaci
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigususpp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Siphonaptera e.g. Xenopsylla cheopis, Ctentocephalides felis, Ceratophyllus spp ..
  • Arachnida for example Scorpio maurus, Latrodectus mactans.
  • Acarina for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Psoroptes Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the active substance combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and Fine encapsulation in polymeric substances.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl
  • Hafit agents such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the active compound combinations according to the invention can be in their commercially available
  • Formulations and in the use forms prepared from these formulations are present in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides or growth-regulating substances.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • the application takes place in a customary manner adapted to the application forms.
  • the active compound combinations according to the invention can be used against all flying and crawling insects and arachnids in all stages of development. They are particularly preferred for controlling fleas and cockroaches, i.e. insects of the Blattariae order, in particular the Blattellidae family, preferably the Blattella germanica species or the Blattidae family, preferably the Blatta orientalis and Periplaneta americana species, but also against other types of cockroaches but preferably against Blattella germanica.
  • fleas and cockroaches i.e. insects of the Blattariae order, in particular the Blattellidae family, preferably the Blattella germanica species or the Blattidae family, preferably the Blatta orientalis and Periplaneta americana species, but also against other types of cockroaches but preferably against Blattella germanica.
  • transfluthrin in addition to its excellent activity against flying insects, is used in aerosol, vaporizer and smoking systems, and is also a very good means of driving hidden vermin such as cockroaches from all stages of development out of their hiding places (flushing effect ). These then come into contact with the freshly created active substance coatings and are killed in the process (K. Naumann, W. Behrenz, EP 279 325 (1988)).
  • the active ingredient can be in a wide variety of formulations, e.g. can be used as a spray can, oil spray, water-based pump spray, ULV, hot and cold mist.
  • formulations based on e.g. Emulsion concentrates (EC), water-based emulsion concentrates (EW) or wettable powders (WP) e.g. Emulsion concentrates (EC), water-based emulsion concentrates (EW) or wettable powders (WP)
  • transfluthrin can also be used as a preparation for combating creeping insects, preferably cockroaches but also fleas, with a long-term effect if this effect is only intended to be brief, in the sense of a few days.
  • the preparation also acts as a residual active ingredient against all stages of development of the cockroaches.
  • Spray cans, oil sprays and pump sprays are suitable.
  • the chitin synthesis inhibitor triflumuron belongs chemically to the group of benzoyl ureas, the effect of which differs fundamentally from that of conventional insecticides such as phosphoric acid esters, carbamates or pyrethroids
  • Triflumuron is not an acute insecticide, but an inhibitor of development that specifically interferes with the molting process of the various larval stages. Since insects do not have an inner skeleton, an outer skin, which is hardened by chitin, gives them the cuticle, the necessary support and external protection. Triflumuron prevents the younger larvae from changing to the next higher larval stage during their development. Often adult insects on the other hand, not affected because they no longer shed. Triflumuron is effective in the larvae of many insects, including cockroaches and fleas.
  • Chitin occurs only in very specific groups of organisms: in addition to arthropods, also in nematodes, fungi and some algae. In contrast, it is not present in vertebrates, which explains the extremely low toxicity of triflumuron in vertebrates.
  • Triflumuron When used in combination with transfluthrin in cockroaches, the expulsion effect, the immediate insecticidal effect when sprayed directly on the animals and a short lasting effect are achieved. Triflumuron has a long-lasting effect against the various larval stages.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active ingredient combinations according to the invention preferably contain 0.001 to 95, particularly preferably 0.01 to 70% by weight of active ingredient mixture of the two
  • Components Preferred is e.g. a ratio in spray cans:
  • transfluthrin 0.005-10.0% by weight triflumuron or flufenoxuron.
  • Active ingredient combinations with a ratio of 0.01-0.2% by weight of transfluthrin: 0.005-1.5% by weight of triflumuron or flufenoxuron are particularly preferred.
  • the active compound combinations according to the invention can also be used in mosquito or smoking spirals, evaporator plates or long-term evaporators, as well as in moth papers, moth pillows or other heat-independent evaporator systems.
  • transfluthrin in the concept of action, transfluthrin can also be used, for example
  • the triflumuron can be replaced by other chitin synthesis inhibitors such as flufenoxuron, methoprene or juvenoids such as fenoxycarb, pyriproxyfen.
  • this pest control concept can also be used in other formulations, such as ULV, hot and cold mist, as well as emulsion concentrates (EC), water-based emulsion concentrates (EW), wettable powders (WP) or microencapsulations (CS ).
  • Aerosols or oil spray agents are preferably used. Aerosol formulations are preferably composed of the active ingredient combinations mentioned, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosene Boiling ranges from about 50 to 250 ° C, dimethylformanide, N-methyl-pyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, further auxiliaries such as emulsifiers such as sorbitan monooleate, oleyl ethoxylate with 3-7 mol ethylene oxide, fatty alcohol ethoxylate, perfume oils such as essential oils, Esters from medium fatty acids with lower alcohols, aromatic carbonyl compounds, optionally stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxies, triethyl orthoformate and, if necessary, the propellant gases such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • the propellant gases such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases
  • the aerosol mixture as a whole is in a suitable, sufficiently pressure-resistant packaging for spray cans.
  • the material of this packaging can be metal (tin-plated iron or aluminum) with or without a separate inner protective lacquer, glass with or without plastic coating and certain plastics are also suitable (e.g. polyamide, polypropylene, PET).
  • the aerosol packaging includes a suitable, automatically closing valve with technical-physical parameters such as optimized for the application
  • the aerosol packaging should preferably be provided with a suitable protective cap.
  • the oil spray formulations differ fundamentally from the aerosol formulations in that no propellant gases are used, since mechanical pumps are generally provided for atomization.
  • the solvents and other auxiliaries used practically do not differ from the agents commonly used in aerosol formulations.
  • the packing material for this formulation is far less critical, since only tightness and resistance to the contents are required.
  • metals such as iron, mainly tinned and / or painted, aluminum, etc. are suitable.
  • Glass and certain plastics such as polyvinyl chloride, polyethylene, polypropylene, PET are also suitable.
  • Deodorized kerosene / mixture of saturated, 19.32 aliphatic hydrocarbons e.g. isododecane
  • Emulsifier Span 80 1.00
  • N-methylpyrrolidone 20.0 Deodorized kerosene 79.20
  • the test was carried out in plastic trays (pricking boxes, type 23, WuH Fernholz GmbH & Co. KG, Meinerzhagen) with the dimensions 40 cm x 60 cm x 6 cm.
  • the filter paper laid out on the floor was fixed with "tesa” ® film 4104. Talc-coated side walls prevented the cockroaches from escaping.
  • the hiding place was placed in the middle of the bowls, in the front third an inverted water-filled weighing jar as a potions and a piece of rusks as food.
  • the hiding height can be varied by exchanging the slider and the side bars.
  • cockroaches of a certain type and stage or sex were placed in each container 24 hours before the start of the test. After this time, all the animals were usually in hiding. This was placed in the fume cupboard and placed in a plastic container measuring 65 cm x 46.5 cm x 30 cm on two glass cylinders (total height 36 cm, diameter 12 cm). From a distance of 30 cm and 36 cm height, 2 g of can contents were sprayed in the direction of the hiding opening.
  • the hiding place was transferred to the plastic shell on a talc-coated glass ring (height 5 cm, diameter 10 cm).
  • the number of cockroaches driven out was up to 5 min. after treatment in one minute, up to 30 min. at five-minute intervals and after 60 minutes. and determined 24 hours.
  • a kinked filter disc with a diameter of 9.5 cm was placed in the pricking boxes as protection for the expelled cockroaches. Control treatment with an active substance-free dose was carried out in each test. Only in isolated cases did cockroaches drive out of the hiding place again; usually they fell soon from the hiding place.
  • the hiding places were unscrewed, prewashed with acetone, cleaned in the dishwasher at 95 ° C. and dried in a drying cabinet at 150 ° C.
  • the tests are carried out in a fume cupboard in which the suction is to be regulated so that the spray jet is not impaired.
  • One cockroach is placed in a wire gauze box with an inside diameter of 70 mm, a height of 10 mm and a mesh size of 1.5 mm.
  • the test vessels prepared in this way are clamped on the spray apparatus at an angle of 45 °.
  • the area behind and under the gauze test container is lined with absorbent filter paper, which is replaced after each test.
  • the spray can is clamped on the spray apparatus so that the spray jet hits the wire gauze perpendicularly.
  • the time that has to be sprayed before the can content to be applied can be determined from the can to be tested.
  • the can is weighed before and after each test to determine the exact amount applied.
  • a stopwatch is operated at the same time as the spray valve in order to have the knockdown effect to be able to precisely identify the animals.
  • the animals are transferred to a clean container, provided with a swab and evaluated for knock down according to time and% mortality after certain times.
  • Spray volume 2.4 - 2.8 g can content / cockroach from temperature: 22 ° C at a distance of 60 cm rel. Humidity: 47%
  • Test method for testing spray cans for their residual effects against crawling insects
  • the treatment is carried out in a fume cupboard in which the suction can be regulated in such a way that the spray jet is impaired
  • the chamber is lined with filter paper on the floor and on the walls up to a height of 65 cm.
  • the most important materials can be treated, in particular glazed and unglazed tiles, PVC sheets, lacquered plywood, etc.
  • each spray can can differ in its spray behavior (pressure, spray cone, droplet size) from different compositions and technical equipment, the test operator must train with each spray can on cardboard pads (15 x 15 cm), from which distance and before the actual documents are treated at what speed spraying is required.
  • a uniform spraying of the documents with the desired application rate is achieved if, depending on the spray cone and pressure of the spray can, spraying from a distance of 25 - 40 cm. It has proven to be expedient to guide the can in a semicircle by hand.
  • the spray jet is guided on the base from the top left, starting from the center right to the bottom left (Fig. 2).
  • the amount that is sprayed beyond the edges of the underlay, the spray loss, was determined in extensive tests with cardboard borders and was approximately 10%.
  • the spray can is weighed in order to determine the amount of can applied.
  • Spray pads are transferred to the documents in the test room.
  • the treated documents are filled with 5 cockroaches each, which are held in talcum-coated glass rings (diameter 9.5 cm, height 5.5 cm).
  • the evaluation is made for 100% knock down or mortality after 15, 30 and 60 minutes and after 2, 3 and 4 hours.
  • the tests were carried out on one day old and 8, 15, 22, 29, 43, 57, 85 and 113 day aged surfaces.
  • Hiding height 0.5 cm Average from three tests Hiding depth: 5.0 cm Temperature 21 ° C Relative humidity: 48% Spray quantity: 1.9-2.0 g can content
  • Spray quantity 2.4 - 2.8 g can content / cockroach from a distance of 60 cm
  • Spray quantity / 20 m 3 8.7-9.1 g spray time: 4.3-9.1 s
  • the treatment is carried out in a chapel in which the suction can be regulated so that there is no impairment of the spray jet of the cans.
  • the chapel is lined with filter paper on the floor.
  • the most important materials can be treated, in particular glazed and non-glazed tiles, PVC panels, lacquered plywood, etc.
  • a uniform spraying of the documents with the desired application rate is achieved if, depending on the spray cone and pressure of the spray can, spraying is carried out from a distance of 25-40 cm. It has proven to be expedient to guide the can in a semicircle by hand.
  • the spray jet is guided on the base from the top left, starting from the center right to the bottom left (see Fig. 2).
  • the amount that is sprayed beyond the edges of the underlay, the spray loss, was determined in extensive tests with cardboard borders and was approximately 10%.
  • the spray can is weighed in order to determine the amount of can applied.
  • a can content 25 g / m 2 , for example, 0.64 g can content / 225 cm 2 must be applied. This amount already contains the 10% spray loss determined.
  • the freshly treated but still moist substrates are populated with the test animals (cockroaches).
  • test animals are kept on the supports in talcum-coated glass rings (diameter 9.5 cm, height 5.5 cm).
  • rings are placed one on top of the other. Depending on the size, 5 to 10 animals are used per pad. Fleas are kept in non-talcum-coated glass rings.
  • the species Blattella germanica and Blatta orientalis are used for cockroaches.

Abstract

The invention concerns novel active substance combinations of pyrethroids with insect-development inhibitors for achieving a long-term pesticidal effect. These active substance combinations are highly effective, have few environmentally harmful properties, and a combating effect which is advantageous from the toxicological point of view.

Description

Wirkstoffkombinationen aus Pyrethroiden und Insekten-Entwicklungs- hemmernActive ingredient combinations of pyrethroids and insect development inhibitors
Die vorliegende Erfindung betrifft neue Wirkstoffkombinationen von Pyrethroiden mit Insekten-Entwicklungshemmern, zur Erzielung einer Langzeitwirkung gegen tierische Schädlinge, insbesondere Insekten und Spinnentiere, mit hoher Effekti¬ vität, weniger umweltbelastenden Eigenschaften sowie einem toxikologisch günstigen Bekämpfungskonzept.The present invention relates to new active substance combinations of pyrethroids with insect development inhibitors, in order to achieve a long-term action against animal pests, in particular insects and arachnids, with high effectiveness, less environmentally harmful properties and a toxicologically favorable control concept.
Kombinationen von unterschiedlichen insektiziden Mitteln werden zurCombinations of different insecticidal agents are used
Bekämpfung von Insekten in Innenräumen seit langer Zeit angewandt. Dabei werden gewöhnlich insektizide Verbindungsklassen miteinander kombiniert, die keine Kreuzresistenzen aufweisen. Auf diese Weise erhält man Formulierungen, die auch gegen resistente Spezies eine gute Wirkung aufweisen (W. Behrenz, K. Naumann, Pflanzenschutz-Nachrichten Bayer, 35, 309 (1982)).Fighting insects used indoors for a long time. Insecticidal classes of compounds that do not show cross-resistance are usually combined. In this way, formulations are obtained which also have a good action against resistant species (W. Behrenz, K. Naumann, Plant Protection News Bayer, 35, 309 (1982)).
Um einen Austreib-Effekt und sofortige Wirkung ("Knockdown-Wirkung") sowie Langzeitwirkung gegen Insekten ("Residualwirkung") zu erhalten, wurden bisher Phosphorsäureester, Carbamate und langzeitstabile Pyrethroide miteinander kom¬ biniert (C. Fest, K.-J. Schmidt, The Chemistry of Organophosphorus Pesticides, Springer- Verlag, Berlin (1982); W. Behrenz, E.Böcker, PflanzenschutznachrichtenIn order to obtain an expulsion effect and an immediate effect ("knockdown effect") and long-term effect against insects ("residual effect"), phosphoric acid esters, carbamates and long-term stable pyrethroids have been combined to date (C. Fest, K.-J. Schmidt , The Chemistry of Organophosphorus Pesticides, Springer-Verlag, Berlin (1982); W. Behrenz, E. Boecker, Plant Protection News
Bayer, 18, 53 (1965); I. Hammann, R. Fuchs, ibid. 34, 123 (1981) und dort zitierte Literatur).Bayer, 18, 53 (1965); I. Hammann, R. Fuchs, ibid. 34, 123 (1981) and literature cited there).
In letzter Zeit sind nun verschiedene Entwicklungshemmer von Insekten bekannt geworden. Dabei handelt es sich um sogenannte Juvenilhormone sowie um Chitinsynthese-Hemmer aus der Klasse der Benzoylharnstoffe, die den Ent¬ wicklungszyklus von Insekten spezifisch beeinflussen, indem sie die Umwandlung der einzelnen Larvenstadien in die nächsthöheren Entwicklungsstadien verhindern.Various insect development inhibitors have recently become known. These are so-called juvenile hormones and chitin synthesis inhibitors from the benzoyl urea class, which specifically influence the development cycle of insects by preventing the conversion of the individual larval stages into the next higher development stages.
Dieses Wirkprinzip ist speziell den Insekten eigen und kommt im Warmblüter nicht vor. Daraus resultiert neben einer äußerst effektiven Unterbindung der Entwicklung neuer Insektengenerationen auch das völlige Fehlen von Neben¬ wirkungen auf den Warmblüter, wodurch ein toxikologisch günstiges Bekämpfungskonzept erreicht wird. Allerdings haben derartige Entwicklungs¬ hemmer keine Wirkung auf adulte Stadien von Insekten, so daß die Wirkung erst nach einer Wartezeit von bis zu zwei Wochen eintritt. Für eine gezielte Bekämpfung von Schädlingen, insbesondere Insekten und Spinnentieren, müssen daher Insektizide gefunden werden, die zusammen mit Entwicklungshemmern einerseits einen Austreib (flushing-effect) und eine sofortige Wirkung ("Knockdown- Wirkung") zeigen, andererseits aber auch mit einer Langzeitwirkung (Residualwirkung) über mehrere Entwicklungsstadien der Schädlinge hinweg aufwarten, weshalb sich beide Wirkstoffe in optimaler Weise ergänzen müssen.This principle of action is specific to insects and does not occur in warm-blooded animals. In addition to an extremely effective prevention of the development of new generations of insects, this also results in the complete absence of side effects on the warm-blooded animals, as a result of which a toxicologically favorable control concept is achieved. However, such development inhibitors have no effect on adult stages of insects, so that the effect only occurs after a waiting period of up to two weeks. For a targeted Combating pests, especially insects and arachnids, insecticides must therefore be found which, together with development inhibitors, have an expulsion (flushing effect) and an immediate effect ("knockdown effect"), but also a long-term effect (residual effect) there are several stages of development of the pests, which is why both active ingredients have to complement each other in an optimal way.
Überraschend wurde nun gefunden, daß durch die Kombination von synthetischen Pyrethroiden oder natürlichem Pyrethrum, die sich als Einzelwirkstoff durch gute Knockdown-Eigenschaften und einen guten Austreib-Effekt auszeichnen, aber nur bis zu wenigen Tagen wirken, mit Insekten-Entwicklungshemmern eine Langzeit¬ wirkung mit ausgezeichneter Effektivität, weniger umweltbelastenden Eigen¬ schaften sowie toxikologisch günstigerem Bekämpfungskonzept erreichen läßt.Surprisingly, it has now been found that the combination of synthetic pyrethroids or natural pyrethrum, which as a single active ingredient is distinguished by good knockdown properties and a good expulsion effect, but which only work for up to a few days, has a long-term effect with insect development inhibitors excellent effectiveness, less polluting properties and toxicologically more favorable control concept.
Bevorzugt werden als Pyrethroide das Pyrethrum, Allethrin oder Transfluthrin, als Insekten-Entwicklungshemmer Insektizide und Chitinsynthesehemmer, wie z.B. Lufenuron,Pyrethrum, allethrin or transfluthrin are preferred as pyrethroids, insecticides and chitin synthesis inhibitors, such as e.g. Lufenuron,
RH 5849 (2-Benzoyl-l-(l,l-dimethylethylbenzoesäurehydrazid), Chlorfluazuron, Difiubenzuron, N-[[[3,5-Dichlor-4-(4-chlorphenoxy)phenyl]amino]carbonyl], 2,6- difluorbenzamid; Flufenoxuron; Flucycloxuron; Penfluron; Teflubenzuron; Hexaflumuron; Tebufenozide; 2-Chlor-N-[[[4-(l-phenylethoxy)-phenyl]-amino]- carbonyl]-benzamid; Natrium- l,4-bis-(2-ethylhexyl)-sulfobutandioat; Novaluron, 2-RH 5849 (2-benzoyl-l- (l, l-dimethylethylbenzoic acid hydrazide), chlorofluazuron, difiubenzuron, N - [[[3,5-dichloro-4- (4-chlorophenoxy) phenyl] amino] carbonyl], 2,6- difluorobenzamide; flufenoxuron; flucycloxuron; penfluron; teflubenzuron; hexaflumuron; tebufenozide; 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide; sodium 1,4-bis- (2-ethylhexyl) sulfobutanedioate; novaluron, 2-
Chlor-N-[[[4-(2,2-dichlor-l,l-difluorethoxy)-phenyl]-amino]-carbonyl]-benzamid; 6-Azido-N-cyclopropyl-N'-ethyl- 1 ,3,5-triazin-2,4-diamin; N-[[[5-(4-bromphenyl)- 6-methyl-2-pyrazinyl]-amino]-carbonyl]-2,6-dichlorobenzamid; 2,6-Dichlor-N-[[(4- chlorophenyl)amino]-carbonyl]-benzamid; Methoprene; Triflumuron; Pyriproxifen; Fenoxycarb eingesetzt.Chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) phenyl] amino] carbonyl] benzamide; 6-azido-N-cyclopropyl-N'-ethyl-1,3,5-triazine-2,4-diamine; N - [[[5- (4-bromophenyl) 6-methyl-2-pyrazinyl] amino] carbonyl] -2,6-dichlorobenzamide; 2,6-dichloro-N - [[(4-chlorophenyl) amino] carbonyl] benzamide; Methoprene; Triflumuron; Pyriproxifene; Fenoxycarb used.
Besonders bevorzugte Wirkstoffkombinationen bestehen aus Transfluthrin, Allethrin oder Pyrethrum einerseits und aus Fenoxycarb, Pyriproxyfen, Triflumuron, Flufenoxuron und/oder Methoprene andererseits.Particularly preferred combinations of active ingredients consist of transfluthrin, allethrin or pyrethrum on the one hand and fenoxycarb, pyriproxyfen, triflumuron, flufenoxuron and / or methoprene on the other.
Ganz besonders bevorzugt sind Wirkstoffkombinationen bestehend aus Transfluthrin der Formel (I) und Triflumuron der Formel (II) und/oderCombinations of active substances consisting of transfluthrin of the formula (I) and triflumuron of the formula (II) and / or are very particularly preferred
Flufenoxuron. Die Kombination der Wirkstoffe vereint in ausgezeichneter Weise hervorragende Knockdown- und Austreibewirkung mit einer Residualwirkung über mehrere Wochen ohne WirkungslückeFlufenoxuron. The combination of the active ingredients combines in an excellent way Excellent knockdown and expulsion effect with a residual effect over several weeks without a gap in effect
CONK+CONH-C' y— OCF3
Figure imgf000005_0001
(I) (II) Weiterhin zeigt insbesondere die Wirkstoffkombination bestehend aus
CONK + CONH-C'y— OCF 3
Figure imgf000005_0001
(I) (II) Furthermore, the active substance combination consisting of
Transfluthrin der Formel (I) und Flufenoxuron (III) überraschenderweise einen synergistischen Effekt.Transfluthrin of formula (I) and flufenoxuron (III) surprisingly have a synergistic effect.
Figure imgf000005_0002
Figure imgf000005_0002
Dieser Effekt ist dadurch gekennzeichnet, daß die dem Transfluthrin eigene charakteristische Wirkung durch Zusatz von Flufenoxuron verstärkt wird. DerThis effect is characterized in that the characteristic effect inherent in transfluthrin is enhanced by the addition of flufenoxuron. The
Zusatz von Flufenoxuron zu Transfluthrin verstärkt sowohl die Aerosol Wirkung gegen fliegende Insekten als auch die Wirkung nach Direktbesprühung von Schaben und den Austreib eff ekt. Besonders deutlich ist die Verstärkung der Wirkung auf Schaben, die auf frisch besprühten Oberflächen zu beobachten ist.Addition of flufenoxuron to transfluthrin increases both the aerosol effect against flying insects and the effect after direct spraying of cockroaches and the expulsion effect. The increase in the effect on cockroaches, which can be observed on freshly sprayed surfaces, is particularly evident.
Die erfindungsgemäßen Wirkstoffkombinationen eignen sich zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten und Spinnentieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hy¬ gienesektor vorkommen. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie sind gegen normalsensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten tierischenThe active compound combinations according to the invention are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. To the animal mentioned above
Schädlingen gehören:Pests include:
Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgäre, Por¬ cellio scaber. Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Por¬ cellio scaber. From the order of the Diplopoda, for example, Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spec.From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.
Aus der Ordnung der Symphyla z.B. Scuügerella immaculata.From the order of the Symphyla e.g. Scuügerella immaculata.
Aus der Ordnung der Thysanura z.B. Lepisma saccharina.From the order of the Thysanura e.g. Lepisma saccharina.
Aus der Ordnung der Collembola z.B. Onychiurus armatus.From the order of the Collembola e.g. Onychiurus armatus.
Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
Aus der Ordnung der Dermaptera z.B. Forficula auricularia.From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Isoptera z.B. Reticulitermes spp..From the order of the Isoptera e.g. Reticulitermes spp ..
Aus der Ordnung der Anoplura z.B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.From the order of the anoplura e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.
Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius,From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae,From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigususpp. Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus s. From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella sppber, Bucculisellappl ., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae,
Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophana piferosellaella, pellellaella pianosella pellaella, Hofmannophila pseudosella , Clysia ambiguella, Homona magnanima, Tortrix viridana.
Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephususpp sulcatus, Cosmopolites sordidus,
Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Agribiole spp., Tenebrio molitor. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,
Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ctentocephalides felis, Ceratophyllus spp..From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ctentocephalides felis, Ceratophyllus spp ..
Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans. Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp..From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans. From the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Psoroptes Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
Die erfindungsgemäßen Wirkstoffkombinationen können in die üblichen Formu¬ lierungen überführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspen¬ sionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions- Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen.The active substance combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and Fine encapsulation in polymeric substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Ver¬ mischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeu- genden Mitteln.These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasser- Stoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Koh¬ lenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclo¬ hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethyl- sulfoxid, sowie Wasser.If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage: z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fett- säure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylaryl-polyglykolether, Al- kylsulfonate, Alkylsulfate, Arylsulfonate sowie Einweißhydrolysate; als Dispergier- mittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.The following are suitable as solid carriers: for example ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Hafitmittel wie Carboxymethylcellulose, natür¬ liche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Hafit agents such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo- cyaninfarb Stoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die erfindungsgemäßen Wirkstoffkombinationen können in ihren handelsüblichenThe active compound combinations according to the invention can be in their commercially available
Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungs¬ formen in Mischung mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akariziden, Nematiziden, Fungiziden oder wachstums¬ regulierenden Stoffen vorliegen. Zu den Insektiziden zählen beispielsweise Phos- phorsäureester, Carbamate, Carbonsäureester, chlorierte Kohlenwasserstoffe, Phe- nylharnstoffe, durch Mikroorganismen hergestellte Stoffe u.a.Formulations and in the use forms prepared from these formulations are present in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides or growth-regulating substances. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise.The application takes place in a customary manner adapted to the application forms.
Die erfindungsgemäßen Wirkstoffkombinationen können prinzipiell gegen alle fliegenden und kriechenden Insekten und Spinnentiere in allen Entwicklungs¬ stadien eingesetzt werden. Besonders bevorzugt werden sie bei der Bekämpfung von Flöhen und Schaben, also Insekten der Ordnung Blattariae, insbesondere der Familie Blattellidae, vorzugsweise der Art Blattella germanica oder der Familie Blattidae, vorzugsweise der Arten Blatta orientalis und Periplaneta americana, aber auch gegen andere Schabenarten, ganz besonders bevorzugt jedoch gegen Blattella germanica, eingesetzt werden. So ist beispielsweise Transfluthrin neben seiner hervorragenden Wirkungs¬ eigenschaft gegen fliegende Insekten, in Aerosol-, Verdampfer- und Räucher¬ systemen eingesetzt, auch ein sehr gutes Mittel, um versteckt sitzendes Ungeziefer wie z.B. Schaben aller Entwicklungsstadien aus ihren Verstecken zu treiben (flushing-effect). Diese kommen dann mit den frisch geschaffenen Wirkstoff¬ belägen in Berührung und werden dabei abgetötet (K. Naumann, W. Behrenz, EP 279 325 (1988)).In principle, the active compound combinations according to the invention can be used against all flying and crawling insects and arachnids in all stages of development. They are particularly preferred for controlling fleas and cockroaches, i.e. insects of the Blattariae order, in particular the Blattellidae family, preferably the Blattella germanica species or the Blattidae family, preferably the Blatta orientalis and Periplaneta americana species, but also against other types of cockroaches but preferably against Blattella germanica. For example, transfluthrin, in addition to its excellent activity against flying insects, is used in aerosol, vaporizer and smoking systems, and is also a very good means of driving hidden vermin such as cockroaches from all stages of development out of their hiding places (flushing effect ). These then come into contact with the freshly created active substance coatings and are killed in the process (K. Naumann, W. Behrenz, EP 279 325 (1988)).
Werden Insekten, z.B. Schaben oder Flöhe direkt mit Transfluthrin angesprüht, so fallen diese schnell in Rückenlage (knock down) und können sich nicht wieder erholen (Mortalität). Um solche Wirkungen zu erreichen, kann der Wirkstoff in den verschiedensten Formulierungen wie z.B. als Sprühdose, Ölsprühmittel, wasserbasierendes Pumpspray, ULV-, Heiß-und Kaltnebel eingesetzt werden. Desweiteren eignen sich Formulierungen auf Basis von z.B. Emulsions¬ konzentraten (EC), Emulsionskonzentraten auf Wasserbasis (EW) oder wettable powders (WP)If insects, e.g. Cockroaches or fleas sprayed directly with Transfluthrin, they quickly fall on their back (knock down) and cannot recover (mortality). In order to achieve such effects, the active ingredient can be in a wide variety of formulations, e.g. can be used as a spray can, oil spray, water-based pump spray, ULV, hot and cold mist. Furthermore, formulations based on e.g. Emulsion concentrates (EC), water-based emulsion concentrates (EW) or wettable powders (WP)
Über die aufgezeigte Wirkung hinaus, kann Transfluthrin auch als Präparat zur Bekämpfung von kriechenden Insekten, vorzugsweise Schaben aber auch Flöhen, mit Dauerwirkung eingesetzt werden, wenn diese Wirkung nur kurz, im Sinne von einigen Tagen, sein soll. Das Präparat wirkt auch als Residualwirkstoff angewandt gegen alle Entwicklungsstadien der Schaben. Hierfür sind für den nicht professionellen Anwender besonders gut z.B. Sprühdosen, Ölsprühmittel und Pumpsprays geeignet.In addition to the effect shown, transfluthrin can also be used as a preparation for combating creeping insects, preferably cockroaches but also fleas, with a long-term effect if this effect is only intended to be brief, in the sense of a few days. The preparation also acts as a residual active ingredient against all stages of development of the cockroaches. For the non-professional user, e.g. Spray cans, oil sprays and pump sprays are suitable.
Der Chitinsynthesehemmer Triflumuron gehört chemisch zur Gruppe der Benzoyl- harnstoffe, deren Wirkung sich grundlegend von der herkömmlicher Insektizide wie Phosphorsäureester, Carbamate oder Pyrethroide unterscheidetThe chitin synthesis inhibitor triflumuron belongs chemically to the group of benzoyl ureas, the effect of which differs fundamentally from that of conventional insecticides such as phosphoric acid esters, carbamates or pyrethroids
(K. Mrusek in Proc. lst Int. Conf. Insect Pests in the Urban Environment, Hrsg. K.B. Wildey und W.H. Robinson, 1993, 385).(K. Mrusek in Proc. L st Int. Conf. Insect Pests in the Urban Environment, ed. KB Wildey and WH Robinson, 1993, 385).
Triflumuron ist kein akut wirkendes Insektizid, sondern ein Entwicklungshemmer, der spezifisch in den Häutungsvorgang der verschiedenen Larvenstadien eingreift. Da Insekten kein inneres Skelett besitzen, verleiht ihnen eine durch Chitin verfestigte Außenhaut, die Kutikula, die nötige Stützung und den äußeren Schutz. Triflumuron verhindert, daß sich die jüngeren Larven in das nächst höhere Larvenstadium während ihrer Entwicklung umwandeln. Adulte Insekten werden hingegen nicht beeinträchtigt, weil diese sich nicht mehr häuten. Triflumuron ist bei den Larven vieler Insekten wirksam zu denen auch Schaben und Flöhe gehören.Triflumuron is not an acute insecticide, but an inhibitor of development that specifically interferes with the molting process of the various larval stages. Since insects do not have an inner skeleton, an outer skin, which is hardened by chitin, gives them the cuticle, the necessary support and external protection. Triflumuron prevents the younger larvae from changing to the next higher larval stage during their development. Become adult insects on the other hand, not affected because they no longer shed. Triflumuron is effective in the larvae of many insects, including cockroaches and fleas.
Chitin kommt nur bei ganz bestimmten Gruppen von Organismen vor: neben Arthropoden auch bei Nematoden, Pilzen und einigen Algen. Bei Wirbeltieren ist es dagegen nicht vorhanden, was die außerordentlich günstige geringe Toxizität von Triflumuron bei Wirbeltieren erklärt.Chitin occurs only in very specific groups of organisms: in addition to arthropods, also in nematodes, fungi and some algae. In contrast, it is not present in vertebrates, which explains the extremely low toxicity of triflumuron in vertebrates.
Bei einer kombinierten Anwendung in der Praxis wird mit Transfluthrin bei Schaben der Austreibeffekt, die insektizide Sofortwirkung bei Direktbesprühung der Tiere und eine kurze Dauerwirkung erreicht. Das Triflumuron bewirkt die lange Dauerwirkung gegen die verschiedenen Larvenstadien.When used in combination with transfluthrin in cockroaches, the expulsion effect, the immediate insecticidal effect when sprayed directly on the animals and a short lasting effect are achieved. Triflumuron has a long-lasting effect against the various larval stages.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
Die erfindungsgegmäßen Wirkstoffkombinationen enthalten vorzugsweise 0,001 bis 95, besonders bevorzugt 0,01 bis 70 Gew.-% Wirkstoffmischung beiderThe active ingredient combinations according to the invention preferably contain 0.001 to 95, particularly preferably 0.01 to 70% by weight of active ingredient mixture of the two
Komponenten. Bevorzugt ist z.B. in Sprühdosen ein Verhältnis:Components. Preferred is e.g. a ratio in spray cans:
0,01 - 0,2 Gew.-% Transfluthrin : 0,005 - 10,0 Gew.-% Triflumuron oder Flufenoxuron. Insbesonders bevorzugt sind Wirkstoffkombinationen mit einem Verhältnis 0,01 - 0,2 Gew.-% Transfluthrin : 0,005 - 1,5 Gew.-% Triflumuron oder Flufenoxuron.0.01-0.2% by weight transfluthrin: 0.005-10.0% by weight triflumuron or flufenoxuron. Active ingredient combinations with a ratio of 0.01-0.2% by weight of transfluthrin: 0.005-1.5% by weight of triflumuron or flufenoxuron are particularly preferred.
Darüber hinaus können die erfindungsgemäßen Wirkstoffkombinationen aber auch in Mücken- bzw. Räucherspiralen, Verdampferplättchen oder Langzeitverdampfer sowie in Mottenpapieren, Mottenkissen oder anderen hitzeunabhängigen Verdampfersystemen angewandt werden.In addition, the active compound combinations according to the invention can also be used in mosquito or smoking spirals, evaporator plates or long-term evaporators, as well as in moth papers, moth pillows or other heat-independent evaporator systems.
Bei dem Wirkungskonzept kann Transfluthrin beispielsweise aber auch durchIn the concept of action, transfluthrin can also be used, for example
Pyrethrum und/oder Allethrin, das Triflumuron durch andere Chitinsynthese¬ hemmer wie z.B. Flufenoxuron, Methoprene oder Juvenoide wie z.B. Fenoxycarb, Pyriproxyfen ersetzt werden. Neben Sprühdosen, Ölsprühmitteln und wasserbasierenden Pumpsprays ist dieses Konzept zur Bekämpfung von Schädlingen auch in anderen Formulierungen anwendbar wie z.B. ULV-, Heiß- und Kaltnebel sowie Emulsionskonzentrate (EC), Emulsionskonzentrate auf Wasserbasis (EW), wettable powders (WP) oder Mikroverkapselungen (CS).Pyrethrum and / or allethrin, the triflumuron can be replaced by other chitin synthesis inhibitors such as flufenoxuron, methoprene or juvenoids such as fenoxycarb, pyriproxyfen. In addition to spray cans, oil sprays and water-based pump sprays, this pest control concept can also be used in other formulations, such as ULV, hot and cold mist, as well as emulsion concentrates (EC), water-based emulsion concentrates (EW), wettable powders (WP) or microencapsulations (CS ).
Bevorzugt werden Aerosole bzw. Ölsprühmittel eingesetzt. Aerosol-Rezepturen setzen sich vorzugsweise zusammen aus den genannten Wirkstoffkombinationen, Lösungsmitteln wie niedere Alkohole (z. B. Methanol, Ethanol, Propanol, Butanol), Ketone (z. B. Aceton, Methylethylketon), Paraffinkohlenwasserstoffe (z. B. Kerosene) mit Siedebereichen von etwa 50 bis 250° C, Dimethylformanid, N- Methyl-pyrrolidon, Dimethylsulfoxid, aromatische Kohlenwasserstoffe wie Toluol, Xylol, Wasser, ferner Hilfsstoffe wie Emulgatoren wie Sorbitanmonooleat, Oleylethoxylat mit 3 - 7 Mol Ethylenoxid, Fettalkoholethoxylat, Parfümöle wie etherische Öle, Ester aus mittleren Fettsäuren mit niederen Alkoholen, aromatische Carbonylverbindungen, gegebenenfalls Stabilisatoren wie Natriumbenzoat, amphotere Tenside, niedere Epoxide, Triethylorthoformiat und im Bedarfsfalle den Treibgasen wie Propan, Butan, Stickstoff, Preßluft, Dimethylether, Kohlendioxid, Distickstoffoxid, bzw. Gemischen aus diesen Gasen.Aerosols or oil spray agents are preferably used. Aerosol formulations are preferably composed of the active ingredient combinations mentioned, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosene) Boiling ranges from about 50 to 250 ° C, dimethylformanide, N-methyl-pyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, further auxiliaries such as emulsifiers such as sorbitan monooleate, oleyl ethoxylate with 3-7 mol ethylene oxide, fatty alcohol ethoxylate, perfume oils such as essential oils, Esters from medium fatty acids with lower alcohols, aromatic carbonyl compounds, optionally stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxies, triethyl orthoformate and, if necessary, the propellant gases such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
Die Aerosol-Mischung als Ganzes befindet sich bei Sprühdosen in einer geeigneten, ausreichend druckfesten Verpackung. Das Material dieser Verpackung kann Metall (Eisen verzinnt oder Aluminium) mit oder ohne separatem Innenschutzlack sein, ferner sind Glas mit oder ohne Kunststoffummantelung und bestimmte Kunststoffe geeignet (z. B. Polyamid, Polypropylen, PET).The aerosol mixture as a whole is in a suitable, sufficiently pressure-resistant packaging for spray cans. The material of this packaging can be metal (tin-plated iron or aluminum) with or without a separate inner protective lacquer, glass with or without plastic coating and certain plastics are also suitable (e.g. polyamide, polypropylene, PET).
Zur Aerosolverpackung gehört ein geeignetes, selbsttätig schließendes Ventil mit für den Anwendungsfall optimierten technisch-physikalischen Parametern wieThe aerosol packaging includes a suitable, automatically closing valve with technical-physical parameters such as optimized for the application
Düsenöffunungen, Düsenart, Dichtungsmaterialien usw.. Zur Sicherung gegen unbeabsichtigtes Betätigen des Ventils ist vorzugsweise die Aerosolverpackung mit einer geeigneten Schutzkappe zu versehen.Nozzle openings, type of nozzles, sealing materials, etc. To protect against unintentional actuation of the valve, the aerosol packaging should preferably be provided with a suitable protective cap.
Die Ölspray-Formulierungen unterscheiden sich von den Aerosolrezepturen grundsätzlich dadurch, daß keine Treibgase verwendet werden, da zur Zerstäubung in der Regel mechanische Pumpen vorgesehen sind. Die zur Anwendung kommenden Lösungsmittel und sonstige Hilfsmittel unterscheiden sich praktisch nicht von den bei Aerosolrezepturen gebräuchlichen Mitteln. Das Packmaterial für diese Formulierungen ist weit weniger kritisch, da grundsätzlich nur Dichtigkeit und Beständigkeit gegen das Füllgut verlangt werden. So sind beispielsweise Metalle wie Eisen, vorwiegend verzinnt und/oder lackiert, Aluminium usw. geeignet. Ferner eignen sich Glas und bestimmte Kunststoffe wie Polyvinylchlorid, Polyethylen, Polypropylen, PET.The oil spray formulations differ fundamentally from the aerosol formulations in that no propellant gases are used, since mechanical pumps are generally provided for atomization. The solvents and other auxiliaries used practically do not differ from the agents commonly used in aerosol formulations. The packing material for this formulation is far less critical, since only tightness and resistance to the contents are required. For example, metals such as iron, mainly tinned and / or painted, aluminum, etc. are suitable. Glass and certain plastics such as polyvinyl chloride, polyethylene, polypropylene, PET are also suitable.
Die Auswahl der jeweiligen Lösungsmittel und sonstigen Zusatzstoffe sowie der Art der Sprühdosen und der Verpackung richtet sich nach den vorhandenen Materialien, nach den speziellen Einsatzbereichen sowie den Anforderungen an die Lagerfähigkeit der Produkte und kann durch den Fachmann unter Anwendung seines Fachwissens und gegebenenfalls mit Hilfe von einfachen allgemein bekannten Untersuchungsmethoden leicht getroffen werden.The selection of the respective solvents and other additives as well as the type of spray cans and the packaging depends on the available materials, the special areas of application and the requirements for the storage life of the products and can be carried out by the specialist using his specialist knowledge and, if necessary, with the help of simple well-known examination methods can be easily taken.
Die Herstellung der erfindungsgemäßen Wirkstoffkombinationen soll anhand der folgenden Beispiele erläutert werden. The preparation of the active compound combinations according to the invention will be explained using the following examples.
Formulierungsbeispiele:Formulation examples:
Sprayformulierung GewichtsteileSpray formulation parts by weight
Transfluthrin 0,05Transfluthrin 0.05
Triflumuron 0,5Triflumuron 0.5
Aceton 40,0Acetone 40.0
Desodoriertes Kerosen/Gemisch gesättigter, 19,32 aliphatischer Kohlenwasserstoffe (z. B. Isododecan)Deodorized kerosene / mixture of saturated, 19.32 aliphatic hydrocarbons (e.g. isododecane)
Parfümöl 0,03Perfume oil 0.03
Stabilisator (Butylenoxid, Triethylorthoformiat) 0,1 Treibmittel: Propan/Butan (25 : 75) 40,00Stabilizer (butylene oxide, triethyl orthoformate) 0.1 blowing agent: propane / butane (25:75) 40.00
Sprayformulierung GewichtsteileSpray formulation parts by weight
Pyrethrine 0,20 Triflumuron 0,5Pyrethrins 0.20 triflumuron 0.5
Aceton 40,0 Desodoriertes Kerosen 19,197Acetone 40.0 Deodorized Kerosen 19.197
Parfümöl 0,003Perfume oil 0.003
Stabilisator (wie Beispiel 1) o,ιStabilizer (as example 1) o, ι
Treibmittel: Propan/Butan (25 : 75) 40,00Propellant: propane / butane (25:75) 40.00
Sprayformulierung GewichtsteileSpray formulation parts by weight
Transfluthrin 0,03Transfluthrin 0.03
Flufenoxuron 0,05Flufenoxuron 0.05
Isopropanol 5,00 Desodoriertes Kerosen 5,00Isopropanol 5.00 Deodorized kerosene 5.00
Emulgator Span 80 1,00Emulsifier Span 80 1.00
Wasser, entmin. 58,92Water, demineralize 58.92
Treibmittel: Propan/Butan (25 : 75) 30,0Propellant: propane / butane (25:75) 30.0
Ölsprühmittelformulierung GewichtsteileOil spray formulation parts by weight
Transfluthrin 0,03Transfluthrin 0.03
Triflumuron 0,5Triflumuron 0.5
N-Methylpyrrolidon 20,0 Desodoriertes Kerosen 79,20N-methylpyrrolidone 20.0 Deodorized kerosene 79.20
Ölsprühmittelformulierung GewichtsteileOil spray formulation parts by weight
Pyrethrine 0,2 Triflumuron 0,5Pyrethrins 0.2 triflumuron 0.5
N-Methylpyrroli don 20,0 Desodoriertes Kerosen 79,30 Prüfung von Sprühdosen auf flushing effect bei SchabenN-Methylpyrroli don 20.0 Deodorized Kerosen 79.30 Testing spray cans for a flushing effect on cockroaches
Die Prüfung erfolgte in Kunststoffschalen (Pikierkästen, Typ 23, W.u.H. Fernholz GmbH & Co. KG, Meinerzhagen) mit den Maßen 40 cm x 60 cm x 6 cm. Das auf dem Boden ausgelegte Filterpapier wurde mit "tesa"® film 4104 fixiert. Talkumierte Seitenwände verhinderten das Entkommen der Schaben. In der Mitte der Schalen wurde das Versteck, im vorderen Drittel ein umgestülptes wassergefülltes Wägegläschen als Tränke sowie ein Stück Zwieback als Nahrung aufgestellt.The test was carried out in plastic trays (pricking boxes, type 23, WuH Fernholz GmbH & Co. KG, Meinerzhagen) with the dimensions 40 cm x 60 cm x 6 cm. The filter paper laid out on the floor was fixed with "tesa" ® film 4104. Talc-coated side walls prevented the cockroaches from escaping. The hiding place was placed in the middle of the bowls, in the front third an inverted water-filled weighing jar as a potions and a piece of rusks as food.
Boden und Deckenplatte des Versteckes bestehen aus mit weißem DD-Lack beschichtetem Aluminium, Seitenstege und Schieber aus Teflon. Senkkopf¬ schrauben und Flügelmuttern halten die Konstruktion zusammen, wobei mittels des Schiebers die gewünschte Verstecktiefe eingestellt wird. Aufbau und Abmessungen des Versteckes sind Fig. 1: [1 = Bodenplatte 15 x 30 x 0,5 cm, 2 = Schieber 13 x 16 x 0,5 cm, 3 = Deckplatte 15 x 15 x 0,5 cm, 4 = Senkkopfschraube mit Flügelmutter, 5 = Seitensteg 1 x 16 x 0,5 cm, 6 = Öffnung] zu entnehmen. DurchThe floor and ceiling of the hiding place consist of aluminum coated with white DD lacquer, side bars and sliders made of Teflon. Countersunk screws and wing nuts hold the construction together, the desired hiding depth being set by means of the slider. Structure and dimensions of the hiding place are Fig. 1: [1 = base plate 15 x 30 x 0.5 cm, 2 = slide 13 x 16 x 0.5 cm, 3 = cover plate 15 x 15 x 0.5 cm, 4 = countersunk screw with wing nut, 5 = side bridge 1 x 16 x 0.5 cm, 6 = opening]. By
Austausch des Schiebers und der Seitenstege kann die Versteckhöhe variiert werden.The hiding height can be varied by exchanging the slider and the side bars.
In jeden Behälter wurden 24 Stunden vor Versuchsbeginn 10 Schaben einer bestimmten Art sowie Stadiums oder Geschlechtes eingesetzt. Nach dieser Zeit befanden sich in der Regel alle Tiere im Versteck. Dieses wurde in den Abzug ge¬ bracht und in einem Kunststoffbehälter mit den Maßen 65 cm x 46,5 cm x 30 cm auf zwei Glaszylinder (Höhe insgesamt 36 cm, Durchmesser 12 cm) gestellt. Aus einer Entfernung von 30 cm und 36 cm Höhe wurden 2 g Doseninhalt in Richtung der Verstecköffnung gesprüht.Twenty-four cockroaches of a certain type and stage or sex were placed in each container 24 hours before the start of the test. After this time, all the animals were usually in hiding. This was placed in the fume cupboard and placed in a plastic container measuring 65 cm x 46.5 cm x 30 cm on two glass cylinders (total height 36 cm, diameter 12 cm). From a distance of 30 cm and 36 cm height, 2 g of can contents were sprayed in the direction of the hiding opening.
Nach Beendigung des Sprühvorganges erfolgte die Übertragung des Versteckes in die Kunststoffschale auf einen talkumierten Glasring (Höhe 5 cm, Durchmesser 10 cm). Die Zahl der ausgetriebenen Schaben wurde bis zu 5 min. nach Behandlung in einminütigem, bis zu 30 min. in fünfminütigem Abstand, sowie nach 60 min. und 24 Stunden ermittelt. Nach 60 min. wurde eine geknickte Filterscheibe mit Durchmesser 9,5 cm als Schutz für die ausgetriebenen Schaben in die Pikierkästen gegeben. In jedem Versuch wurde eine Kontrollbehandlung mit einer wirkstoffreien Dose durchgeführt. Nur in Einzelfällen suchten herausgetriebene Schaben das Versteck nochmals auf; in der Regel fielen sie bald vom Versteck herunter. Nach Versuchsabschluß wurden die Verstecke auseinan¬ dergeschraubt, mit Aceton vorgespült, bei 95°C in der Spülmaschine gereinigt und bei 150°C im Trockenschrank getrocknet.After the spraying process was completed, the hiding place was transferred to the plastic shell on a talc-coated glass ring (height 5 cm, diameter 10 cm). The number of cockroaches driven out was up to 5 min. after treatment in one minute, up to 30 min. at five-minute intervals and after 60 minutes. and determined 24 hours. After 60 min. a kinked filter disc with a diameter of 9.5 cm was placed in the pricking boxes as protection for the expelled cockroaches. Control treatment with an active substance-free dose was carried out in each test. Only in isolated cases did cockroaches drive out of the hiding place again; usually they fell soon from the hiding place. After the end of the experiment, the hiding places were unscrewed, prewashed with acetone, cleaned in the dishwasher at 95 ° C. and dried in a drying cabinet at 150 ° C.
Tabelle 1Table 1
Austreibeffekt von verschiedenen Sprühdosen gegen Schaben der ArtExpulsion effect of various spray cans against cockroaches of the kind
Blattella germanica L 5Blattella germanica L 5
Versteckhöhe: 0,5 cm Mittel aus 2 Versuchen Temperatur: 21°C Verstecktiefe: 5,0 cm rel. Feuchte: 55 % Sprühmenge: 2,0 - 2,2 g DoseninhaltHiding height: 0.5 cm Average from 2 experiments Temperature: 21 ° C Hiding depth: 5.0 cm rel. Moisture: 55% spray quantity: 2.0 - 2.2 g can content
Figure imgf000016_0001
Figure imgf000016_0001
Prüfung von Sprühdosen auf Wirkung nach Direktbesprühung von kriechenden Insekten.Testing spray cans for effects after direct spraying of crawling insects.
Die Versuche werden in einer Abzugskammer durchgeführt, in der die Absaugung so zu regulieren ist, daß eine Beeinträchtigung des Sprühstrahls nicht erfolgt.The tests are carried out in a fume cupboard in which the suction is to be regulated so that the spray jet is not impaired.
Jeweils eine Schabe wird in eine Drahtgazebox mit einem Innendurchmesser von 70 mm, einer Höhe von 10 mm und einer Maschenweite von 1,5 mm gesetzt. Die so vorbereiteten Versuchsgefäße werden an der Sprühapparatur in einem Winkel von 45° eingespannt. Die Fläche hinter und unter dem Gazeprüfbehälter wird mit saugfähigem Filterpapier ausgelegt, das nach jeder Prüfung ausgetauscht wird.One cockroach is placed in a wire gauze box with an inside diameter of 70 mm, a height of 10 mm and a mesh size of 1.5 mm. The test vessels prepared in this way are clamped on the spray apparatus at an angle of 45 °. The area behind and under the gauze test container is lined with absorbent filter paper, which is replaced after each test.
In einer Entfernung von 60 cm in der Mitte der Drahtgaze bis zur Düse des Sprühkopfes der zu prüfenden Aerosole gerechnet, wird an der Sprühapparatur die Sprühdose so eingespannt, daß der Sprühstrahl senkrecht auf die Drahtgaze trifft. Von der zu prüfenden Dose wird vorher die Zeit ermittelt, die gesprüht werden muß, um 2,4 - 2,8 g Doseninhalt auszubringen. Vor und nach jedem Versuch wird die Dose gewogen, um die ausgebrachte Menge exakt zu bestimmen. Gleichzeitig mit dem Sprühventil wird eine Stoppuhr betätigt, um die Knockdown- Wirkung auf die Tiere genau bestimmen zu können. Die Tiere werden gleich nach dem Besprühen in ein sauberes Gefäß überführt, mit einem Tupfer versehen und auf knock down nach Zeit sowie % Mortalität nach bestimmten Zeiten ausgewertet.Calculated at a distance of 60 cm in the middle of the wire gauze to the nozzle of the spray head of the aerosols to be tested, the spray can is clamped on the spray apparatus so that the spray jet hits the wire gauze perpendicularly. The time that has to be sprayed before the can content to be applied can be determined from the can to be tested. The can is weighed before and after each test to determine the exact amount applied. A stopwatch is operated at the same time as the spray valve in order to have the knockdown effect to be able to precisely identify the animals. Immediately after spraying, the animals are transferred to a clean container, provided with a swab and evaluated for knock down according to time and% mortality after certain times.
Tabelle 2Table 2
Wirkung von verschiedenen Sprühdosen nach Direktbesprühung von . Schaben der Art Blattella germanica mmEffect of different spray cans after direct spraying of. Cockroaches of the species Blattella germanica mm
Sprühmenge: 2,4 - 2,8 g Doseninhalt/Schabe aus Temperatur: 22°C einer Entfernung von 60 cm rel. Feuchte: 47 %Spray volume: 2.4 - 2.8 g can content / cockroach from temperature: 22 ° C at a distance of 60 cm rel. Humidity: 47%
(Mittel aus 10 Versuchen)(Average of 10 attempts)
Figure imgf000017_0001
Figure imgf000017_0001
Testmethode zur Prüfung von Sprühdosen auf ihre Residualwirkung gegen kriechende Insekten.Test method for testing spray cans for their residual effects against crawling insects.
1. Besprühen der Unterlagen1. Spraying the documents
Die Behandlung wird in einer Abzugskammer durchgeführt, in der sich die Absaugung so regulieren läßt, daß eine Beeinträchtigung des Sprühstrahls derThe treatment is carried out in a fume cupboard in which the suction can be regulated in such a way that the spray jet is impaired
Dosen nicht erfolgt. Die Kammer wird auf dem Boden und an den Wänden bis zu einer Höhe von 65 cm mit Filterpapier ausgekleidet.Cans not done. The chamber is lined with filter paper on the floor and on the walls up to a height of 65 cm.
Behandelt werden können die wichtigsten Materialien, insbesondere lasierte und unlasierte Kacheln, PVC-Platten, lackiertes Sperrholz usw.. Die zu behandelnden Unterlagen (Größe 15 x 15 cm = 225 cm2) werden auf einem StativringThe most important materials can be treated, in particular glazed and unglazed tiles, PVC sheets, lacquered plywood, etc. The documents to be treated (size 15 x 15 cm = 225 cm 2 ) are placed on a tripod ring
(Durchmesser außen 10 cm), der in einer Höhe von 5 cm an einem Stativ befestigt ist, so aufgestellt und an der Stativstange angelehnt, daß ein Winkel von 55° gebildet wird. Da jede Sprühdose von unterschiedlicher Zusammensetzung und technischer Ausrüstung in ihrem Sprühverhalten (Druck, Spritzkegel, Tröpfchengröße) abweichen kann, muß der Versuchsansteller, bevor die eigentlichen Unterlagen behandelt werden, mit jeder Sprühdose an Pappunterlagen (15 x 15 cm) trainieren, aus welcher Entfernung und in welcher Geschwindigkeit gesprüht werden muß.(Outside diameter 10 cm), which is attached to a tripod at a height of 5 cm, set up and leaned against the tripod rod so that an angle of 55 ° is formed. Since each spray can can differ in its spray behavior (pressure, spray cone, droplet size) from different compositions and technical equipment, the test operator must train with each spray can on cardboard pads (15 x 15 cm), from which distance and before the actual documents are treated at what speed spraying is required.
Ein gleichmäßiges Besprühen der Unterlagen mit der gewünschten Aufwandmenge wird erreicht, wenn je nach Spritzkegel und Druck der Sprühdose aus einer Entfernung von 25 - 40 cm gesprüht wird. Dabei hat es sich als zweckmäßig erwiesen, die Dose von Hand in einem Halbkreis zu führen. Der Sprühstrahl wird dabei auf der Unterlage oben links beginnend über Mitte rechts nach unten links geführt (Fig. 2).A uniform spraying of the documents with the desired application rate is achieved if, depending on the spray cone and pressure of the spray can, spraying from a distance of 25 - 40 cm. It has proven to be expedient to guide the can in a semicircle by hand. The spray jet is guided on the base from the top left, starting from the center right to the bottom left (Fig. 2).
Die Menge, die über die Ränder der Unterlagen hinaus gesprüht wird, der Spritzverlust, wurde in eingehenden Versuchen mit Pappumrandungen bestimmt und betrug ca. 10 %.The amount that is sprayed beyond the edges of the underlay, the spray loss, was determined in extensive tests with cardboard borders and was approximately 10%.
Vor und nach jedem Sprühvorgang wird die Sprühdose gewogen, um die ausgebrachte Menge Doseninhalt zu bestimmen.Before and after each spraying process, the spray can is weighed in order to determine the amount of can applied.
Um eine Doseninhaltsmenge von 50 g/m2 auszubringen, müssen 1,24 g Doseninhalt/225 cm2 ausgebracht werden. Diese Menge enthält bereits die ermittelten 10 % Spritzverlust.In order to apply a can content of 50 g / m 2 , 1.24 g can content / 225 cm 2 must be applied. This amount already contains the 10% spray loss determined.
Unterlagen, auf die nicht die innerhalb der Toleranz von 1,20 bis 1,30 g liegende Menge Doseninhalt ausgebracht werden, müssen verworfen werden. Sofort nach dem Besprühen wird die Unterlage aus ihrer Schrägstellung genommen und flach gelegt, um ein Ablaufen des Sprühbelages, insbesondere bei nichtsaugenden Unterlagen und extrem feuchten Sprühdosen, zu vermeiden. Nach Abtrocknen derDocuments on which the amount of can contents within the tolerance of 1.20 to 1.30 g are not applied must be discarded. Immediately after spraying, the underlay is taken out of its inclined position and laid flat to prevent the spray coating from running off, especially with non-absorbent underlays and extremely moist spray cans. After drying the
Spritzbeläge werden die Unterlagen in den Testraum überführt. 2. Tiermaterial und TestungSpray pads are transferred to the documents in the test room. 2. Animal material and testing
Die behandelten Unterlagen werden mit je 5 Schaben besetzt, die in talkumierten Glasringen (Durchmesser 9,5 cm, Höhe 5,5 cm) gehalten werden.The treated documents are filled with 5 cockroaches each, which are held in talcum-coated glass rings (diameter 9.5 cm, height 5.5 cm).
Auswertung:Evaluation:
Einen Tag nach der Behandlung, dann nach 2 bis zu 4 Tagen täglich werden die behandelten Unterlagen jeweils mit den Testtieren besetzt.One day after the treatment, then after 2 to 4 days a day, the treated documents are populated with the test animals.
Die Auswertung erfolgt auf 100 % knock down bzw. Mortalität nach 15, 30 und 60 Minuten sowie nach 2, 3 und 4 Stunden.The evaluation is made for 100% knock down or mortality after 15, 30 and 60 minutes and after 2, 3 and 4 hours.
Tabelle 3Table 3
Residualwirkung von verschiedenden Sprühdosen ausgebracht auf lasierten Kacheln (LK) und unlasierten Kacheln (UK) gegen Schaben der ArtResidual effect of various spray cans applied on glazed tiles (LK) and unglazed tiles (UK) against cockroaches of the type
Blattella germanica mm.Blattella germanica mm.
Temperatur : 24-25°C rel. Feuchte: 69-76%Temperature: 24-25 ° C rel. Humidity: 69-76%
Alter der Test¬Age of the test
Unter¬ zeit 0,05 % Transfluthrin 0,05 % Transfluthrin Kontrolle lagen 0,5 % Triflumuron 0,5 % TriflumuronAt present 0.05% transfluthrin 0.05% transfluthrin control 0.5% triflumuron 0.5% triflumuron
LK UK LK UK LK UK LK UK l.Tag 15' 80 0 0 0 20 40 0 0LK UK LK UK LK UK LK UK 1st day 15 '80 0 0 0 20 40 0 0
30' 100 80 0 0 100 100 0 030 '100 80 0 0 100 100 0 0
60' 100 100 0 0 100 100 0 060 '100 100 0 0 100 100 0 0
2 h 100 100 0 0 100 100 0 02 h 100 100 0 0 100 100 0 0
3 h 100 100 0 0 100 100 0 03 h 100 100 0 0 100 100 0 0
4 h 100 100 0 0 100 100 0 04 h 100 100 0 0 100 100 0 0
2 Tage 15' 100 20 0 0 100 20 0 02 days 15 '100 20 0 0 100 20 0 0
30' 100 60 0 0 100 80 0 030 '100 60 0 0 100 80 0 0
60' 100 60 0 0 100 100 0 060 '100 60 0 0 100 100 0 0
2 h 100 100 0 0 100 100 0 02 h 100 100 0 0 100 100 0 0
3 h 100 100 0 0 100 100 0 03 h 100 100 0 0 100 100 0 0
4 h 100 100 0 0 100 100 0 04 h 100 100 0 0 100 100 0 0
3 Tage 15' 0 0 0 0 60 20 0 03 days 15 '0 0 0 0 60 20 0 0
30' 100 0 0 0 80 60 0 030 '100 0 0 0 80 60 0 0
60' 100 40 0 0 100 100 0 060 '100 40 0 0 100 100 0 0
2 h 100 20 0 0 100 80 0 02 h 100 20 0 0 100 80 0 0
3 h 100 40 0 0 100 100 0 03 h 100 40 0 0 100 100 0 0
4 h 100 40 0 0 100 100 0 04 h 100 40 0 0 100 100 0 0
4 Tage 15' 20 0 0 0 20 20 0 04 days 15 '20 0 0 0 20 20 0 0
30' 20 0 0 0 20 20 0 030 '20 0 0 0 20 20 0 0
60' 20 0 0 0 40 20 0 060 '20 0 0 0 40 20 0 0
2 h 40 0 0 0 20 20 0 02 h 40 0 0 0 20 20 0 0
3 h 40 0 0 0 20 20 0 03 h 40 0 0 0 20 20 0 0
4 h 60 0 0 0 20 20 0 0 Zwangskontaktzeittest4 h 60 0 0 0 20 20 0 0 Forced contact time test
Auf den zu prüfenden Unterlagen werden jeweils 5 Larven der Schabenart Blattella germanica eines definierten Stadiums innerhalb von talkumierten Glas¬ ringen (Durchmesser 9,5 cm; Höhe 5,5 cm) ausgesetzt. Durch Entfernen der Tiere nach bestimmten Zeiten, lassen sich unterschiedliche Kontaktzeiten erreichen z.B. 2 x 60 min / Woche (Dienstag und Freitag). Die Larven werden von den Ober¬ flächen genommen, jeweils in glasklare Kunststoffbecher überführt, in denen sich Wasser, Nahrung und ein Versteck befindet (Tablettenröhrchen Durchmesser 1,5 cm, Länge 5,5 cm mit nassem Zellstoff gefüllt, Lupolen-Stopfen mit 425 mg gemahlenem Hundekuchen, 3 fach gefaltetes Filterpapier Durchmesser 7 cm als Versteck) und darin weiter gezüchtet. Die Schaben werden in wöchentlichen Abständen auf Mortalität ausgewertet. Die Temperaturen betragen 22-23 °C, die rel. Luftfeuchte 55-65 % bei 12 stündigem Neonlicht Tag / Nachtrythmus.5 larvae of the cockroach species Blattella germanica of a defined stage are placed on talcum-coated glass rings (diameter 9.5 cm; height 5.5 cm). By removing the animals after certain times, different contact times can be achieved e.g. 2 x 60 min / week (Tuesday and Friday). The larvae are removed from the surfaces, each transferred to a clear plastic beaker in which there is water, food and a hiding place (tablet tube 1.5 cm in diameter, 5.5 cm in length filled with wet cellulose, Lupolen stopper with 425 mg ground dog biscuit, 3 times folded filter paper diameter 7 cm as a hiding place) and further grown in it. The cockroaches are evaluated for mortality at weekly intervals. The temperatures are 22-23 ° C, the rel. Humidity 55-65% with 12 hours of neon light day / night rhythm.
Die Prüfungen erfolgten auf einen Tag alten sowie 8, 15, 22, 29, 43, 57, 85 und 113 Tage lang gealterten Oberflächen.The tests were carried out on one day old and 8, 15, 22, 29, 43, 57, 85 and 113 day aged surfaces.
Tabelle 4Table 4
Residualwirkung von Transfluthrin und Triflumuron alleine und in Kom bination in Sprühdosen auf lasierten Kacheln gegen das 2. Larvenstadium von Blattella germanicaResidual effects of transfluthrin and triflumuron alone and in combination in spray cans on glazed tiles against the second larval stage of Blattella germanica
(Mittel aus 2 Versuchen) Temperatur: 22-23 °C rel. Feuchte: 55-65 % Sprühmenge: 50 g Doseninhalt/m Kontaktzeit: 2 x 1 Stunde/Woche(Average of 2 experiments) temperature: 22-23 ° C rel. Moisture: 55-65% spray quantity: 50 g can content / m contact time: 2 x 1 hour / week
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000020_0001
Figure imgf000021_0001
Tabelle 5Table 5
Residualwirkung von Transfluthrin und Triflumuron alleine und in Kombination in Sprühdosen auf lasierten Kacheln gegen das 3. -4. Larven¬ stadium von Blattella germanicaResidual effects of transfluthrin and triflumuron alone and in combination in spray cans on glazed tiles against the 3rd -4. Larval stage of Blattella germanica
(Mittel aus 2 Versuchen) Temperatur: 22-23 °C rel. Feuchte: 55-65 % Sprühmenge: 50 g Doseninhalt/m2 Kontaktzeit: 2 x 1 Stunde/Woche(Average of 2 experiments) temperature: 22-23 ° C rel. Moisture: 55-65% spray quantity: 50 g can content / m 2 contact time: 2 x 1 hour / week
Figure imgf000022_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Tabelle 6Table 6
Synergistische Verstärkung des Flushing Effekts bei verschiedenen Formulierungen gegen Schaben der Art Blattella germanica L 5Synergistic enhancement of the flushing effect in various formulations against cockroaches of the species Blattella germanica L 5
Versteckhöhe: 0,5 cm Mittel aus drei Versuchen Verstecktiefe: 5,0 cm Temperatur 21°C Relative Feuchte: 48 % Sprühmenge: 1,9-2,0 g DoseninhaltHiding height: 0.5 cm Average from three tests Hiding depth: 5.0 cm Temperature 21 ° C Relative humidity: 48% Spray quantity: 1.9-2.0 g can content
Figure imgf000023_0002
Bei beiden Verstecktiefen ergaben die Versuche, daß Flufenoxuron als Monosprühdose nur eine geringfügige Irritation bei den Schaben hervorrief. Die Kombination von Transfluthrin + Flufenoxuron in den wasserbasierenden Sprühdosen brachte dagegen einen deutlich besseren Austreib eff ekt als die Transfluthrin Mono-Sprühdose.
Figure imgf000023_0002
At both hiding depths, tests showed that flufenoxuron as a single spray can caused only slight irritation in the cockroaches. The combination of transfluthrin + flufenoxuron in the water-based spray cans, on the other hand, resulted in a significantly better expulsion effect than the transfluthrin mono spray can.
Tabelle 7Table 7
Synergistische Verstärkung der Wirksamkeit von verschiedenen Sprühdosen nach Direktbesprühung von Schaben der Art Blattella germanica L 5.Synergistic enhancement of the effectiveness of various spray cans after direct spraying of cockroaches of the species Blattella germanica L 5.
Sprühmenge: 2,4 - 2,8 g Doseninhalt/Schabe aus einer Entfernung von 60 cmSpray quantity: 2.4 - 2.8 g can content / cockroach from a distance of 60 cm
Temperatur: 20°CTemperature: 20 ° C
Relative Feuchte: 50 % (Mittel aus 10 Versuchen)Relative humidity: 50% (average of 10 tests)
Figure imgf000024_0001
Figure imgf000024_0001
Flufenoxuron alleine zeigte in allen 3 Konzentrationen keine Wirkung auf die Schaben. Transfluthrin in Kombination mit Flufenoxuron zeigte bei allen 3 Kombinationen eine deutliche Verbesserung der Wirkung im Vergleich zu Transfluthrin alleine. Mit steigendem Flufenoxuron-Gehalt verbesserte sich die Wirkung, sodaß die Kombination gegenüber der Mono-Sprühdose um den Faktor 2-2,5 fach besser wirkten. Tabelle 8Flufenoxuron alone showed no effect on the cockroaches in all 3 concentrations. Transfluthrin in combination with flufenoxuron showed a significant improvement in the effect in all 3 combinations compared to transfluthrin alone. With increasing flufenoxuron content, the effect improved, so that the combination had a factor of 2-2.5 times better compared to the mono spray can. Table 8
Synergistische Verstärkung der Wirksamkeit verschiedener Aerosolsprühdosen in 20 m'-Kammern gegen Mücken der Art Culex quinquefasciatus, resistent.Synergistic enhancement of the effectiveness of various aerosol spray doses in 20 m 'chambers against mosquitoes of the species Culex quinquefasciatus, resistant.
(Mittel von 3-5 Versuchen) Raumtemperatur: 23,6-24,2°C Sprühmenge/20 cbm: 8,7-9,1 g(Average of 3-5 experiments) Room temperature: 23.6-24.2 ° C spray quantity / 20 cbm: 8.7-9.1 g
Relative Feuchte: 44,9-64,3 % Sprühzeit: 4,3-9,1 sRelative humidity: 44.9-64.3% spraying time: 4.3-9.1 s
Figure imgf000025_0001
Figure imgf000025_0001
Tabelle 9Table 9
Synergistisch e Verstärkung der Wirksam keit verschied ener Aerosolsprühdosen in 20 m3-Kammern gegen Fliegen der Art Musca domestica Stamm WHO(N) mm F 447, sensibelSynergistic increase in the effectiveness of various aerosol spray cans in 20 m 3 chambers against flies of the species Musca domestica strain WHO (N) mm F 447, sensitive
(Mittel von 3-5 Versuchen) Temperatur: 23,6-24,2°C relative Feuchte: 44,9-64,3 %(Average of 3-5 experiments) Temperature: 23.6-24.2 ° C relative humidity: 44.9-64.3%
Sprühmenge/20 m3: 8,7-9,1 g Sprühzeit: 4,3-9,1 sSpray quantity / 20 m 3 : 8.7-9.1 g spray time: 4.3-9.1 s
Figure imgf000026_0001
Figure imgf000026_0001
Tabelle 10Table 10
Synergistisch e Verstärku n g der W irksam keit vers ch ied en er Aerosolsprühdosen in 20 m3-Kammern gegen Fliegen der Art Musca domestica Stamm Weymanns mm F 386, resistent.Synergistic enhancement of the effectiveness of various aerosol spray cans in 20 m 3 chambers resistant to flies of the Musca domestica strain Weymanns mm F 386, resistant.
(Mittel von 3-5 Versuchen) Temperatur: 23,5-24,2°C Relative Feuchte: 40,5-65,3 %(Average of 3-5 attempts) Temperature: 23.5-24.2 ° C Relative humidity: 40.5-65.3%
Sprühmentge/20 cm3 11,7-12,0 g Sprühzeit: 6,2-12,1 sSpray algae / 20 cm 3 11.7-12.0 g spraying time: 6.2-12.1 s
Figure imgf000027_0001
Figure imgf000027_0001
Diese Dose mit 0,01 % Flufenoxuron zeigte wie zu erwarten bei allen geprüften Tierarten keine Wirkung.As expected, this can with 0.01% flufenoxuron had no effect on all tested animal species.
Gegen die resistenten Mücken wirkten die Kombinationsdosen deutlich schneller als die Transfluthrin-Mono-Dose (Tabelle 8).The combination doses acted much faster against the resistant mosquitoes than the transfluthrin mono dose (Table 8).
Bei den sensiblen und resistenten Fliegen wirkten die Kombinations-Dosen schneller als die Transfluthrin-Mono-Dose. Besonders deutlich machte sich dieser Unterschied in der Mortalität bei resistenten Fliegen bemerkbar (Tabellen 9-10). Prüfung von Sprühdosen auf Wirkung von frischen noch feuchten Spritzbelägen gegen Schaben.For the sensitive and resistant flies, the combination doses worked faster than the transfluthrin mono dose. This difference was particularly noticeable in the mortality of resistant flies (Tables 9-10). Testing of spray cans for the effect of fresh, wet spray coatings against cockroaches.
1. Besprühen der Unterlagen1. Spraying the documents
Die Behandlung wird in einer Abzugskapelle durchgeführt, in der sich die Absaugung so regulieren läßt, daß eine Beeinträchtigung des Sprühstrahls der Dosen nicht erfolgt. Die Kapelle wird auf dem Boden mit Filterpapier ausgekleidet.The treatment is carried out in a chapel in which the suction can be regulated so that there is no impairment of the spray jet of the cans. The chapel is lined with filter paper on the floor.
Behandelt werden können die wichtigsten Materialien, insbesondere lasierte und unlasierte Kacheln, PVC-Platten, lackiertes Sperrholz usw. Die zu behandelten Unterlagen (Größe 15 x 15 cm = 225 cm2) werden in einer mit Filterpapier ausgelegten Sprühbox, ein abgesaugter, nach vornehin offener Behälter, in einer Halterung in einem Winkel von 45°C eingelegt. Da jede Sprühdose von unterschiedlicher Zusammensetzung und technischer Ausrüstung in ihrem Sprühverhalten (Druck, Spritzkegel, Tröpfchengröße) abweichen kann, muß der Versuchsansteller, bevor die eigentlichen Unterlagen behandelt werden, mit jeder Sprühdose an Pappunterlagen (15 x 15 cm) trainieren, aus welcher Entfernung und in welcher Geschwindigkeit gesprüht werden muß.The most important materials can be treated, in particular glazed and non-glazed tiles, PVC panels, lacquered plywood, etc. The documents to be treated (size 15 x 15 cm = 225 cm 2 ) are in a spray box lined with filter paper, a vacuumed, open to the start Container placed in a holder at an angle of 45 ° C. Since each spray can can differ in its spray behavior (pressure, spray cone, droplet size) from different compositions and technical equipment, the test operator must train with each spray can on cardboard pads (15 x 15 cm), from which distance and before the actual documents are treated at what speed spraying is required.
Ein gleichmäßiges Besprühen der Unterlagen mit der gewünschten Aufwandmenge wird erreicht, wenn je nach Spritzkegel und Druck der Sprühdose aus einer Entfernung von 25-40 cm gesprüht wird. Dabei hat es sich als zweckmäßig erwiesen, die Dose von Hand in einem Halbkreis zu führen. Der Sprühstrahl wird dabei auf der Unterlage oben links beginnend über Mitte rechts nach unten links geführt (siehe Fig. 2).A uniform spraying of the documents with the desired application rate is achieved if, depending on the spray cone and pressure of the spray can, spraying is carried out from a distance of 25-40 cm. It has proven to be expedient to guide the can in a semicircle by hand. The spray jet is guided on the base from the top left, starting from the center right to the bottom left (see Fig. 2).
Die Menge, die über die Ränder der Unterlagen hinaus gesprüht wird, der Spritzverlust, wurde in eingehenden Versuchen mit Pappumrandungen bestimmt und betrug ca. 10 %.The amount that is sprayed beyond the edges of the underlay, the spray loss, was determined in extensive tests with cardboard borders and was approximately 10%.
Vor und nach jedem Sprühvorgang wird die Sprühdose gewogen, um die ausgebrachte Menge Doseninhalt zu bestimmen. Um eine z.B. Doseninhaltsmenge von 25 g/m2 auszubringen, müssen 0,64 g Doseninhalt/225 cm2 ausgebracht werden. Diese Menge enthält bereits die ermittelten 10 % Spritzverlust.Before and after each spraying process, the spray can is weighed in order to determine the amount of can applied. In order to apply a can content of 25 g / m 2 , for example, 0.64 g can content / 225 cm 2 must be applied. This amount already contains the 10% spray loss determined.
Unterlagen, auf die nicht die innerhalb der Toleranz von 0,59 bis 0,69 g liegende Menge Doseninhalt ausgebracht werden, müssen verworfen werden. Sofort nach dem Besprühen wird die Unterlage aus ihrer Schrägstellung genommen und flach gelegt, um ein Ablaufen des Sprühbelages, insbesondere bei nichtsaugenden Unterlagen und extrem feuchten Sprühdosen, zu vermeiden. Nach Abtrocknen der Spritzbeläge werden die Unterlagen in den Testraum überführt.Documents on which the amount of can contents within the tolerance of 0.59 to 0.69 g are not applied must be discarded. Immediately after spraying, the underlay is taken out of its inclined position and laid flat to prevent the spray coating from running off, especially with non-absorbent underlays and extremely moist spray cans. After the spray coatings have dried, the documents are transferred to the test room.
2. Tiermaterial und Testung2. Animal material and testing
Die frisch behandelten aber noch feuchten Unterlagen werden mit den Testtieren (Schaben) besetzt.The freshly treated but still moist substrates are populated with the test animals (cockroaches).
Die Testtiere werden auf den Unterlagen in talkumierten Glasringen (Duchmesser 9,5 cm, Höhe 5,5 cm) gehalten. Bei Testtieren, die die Höhe des Glasringes überwinden können, werden entsprechend Ringe übereinandergesetzt. Je nach Größe werden 5 bis 10 Tiere pro Unterlage eingesetzt. Flöhe werden in nicht talkumierten Glasringen gehalten.The test animals are kept on the supports in talcum-coated glass rings (diameter 9.5 cm, height 5.5 cm). For test animals that can overcome the height of the glass ring, rings are placed one on top of the other. Depending on the size, 5 to 10 animals are used per pad. Fleas are kept in non-talcum-coated glass rings.
Bei den Schaben werden die Arten Blattella germanica und Blatta orientalis eingesetzt.The species Blattella germanica and Blatta orientalis are used for cockroaches.
3. Auswertung3. Evaluation
Die Auswertung erfolgt auf 20 und 100 % knock down nach Sekunden bzw. Minuten bis zu 2 Stunden. Danach wird prozentual ausgewertet. Tabelle 11The evaluation takes place at 20 and 100% knock down after seconds or minutes up to 2 hours. Then it is evaluated as a percentage. Table 11
Synergistische Verstärkung der Wirksamkeit von Sprühdosen, gemessen auf verschiedenen noch feuchten Oberflächen gegen Schaben der Art Blattella germanica L.5.Synergistic enhancement of the effectiveness of spray cans, measured on various still moist surfaces against cockroaches of the species Blattella germanica L.5.
Temperatur: 21 °C Relative Feuchte: 48 % Sprühmenge: 25 g/m2 Temperature: 21 ° C Relative humidity: 48% spray quantity: 25 g / m 2
Figure imgf000030_0001
Figure imgf000030_0001
Tabelle 12Table 12
Synergistische Verstärkung der Wirksamkeit von Sprühdosen, gemessen auf verschiedenen noch feuchten Oberflächen gegen Schaben der Art Blatta orientalis L 5.Synergistic enhancement of the effectiveness of spray cans, measured on various still moist surfaces against cockroaches of the species Blatta orientalis L 5.
Temperatur: 21°C Relative Feuchte: 48 % Sprühmenge: 25 g/m2 Temperature: 21 ° C Relative humidity: 48% spray quantity: 25 g / m 2
Figure imgf000031_0001
Figure imgf000031_0001
Die Versuche ergaben, daß Flufenoxuron alleine wie zu erwarten war, gegen beide Schaben Arten, innerhalb der Prüfzeit von 2 Stunden, praktisch keine Wirkung zeigte.The tests showed that flufenoxuron alone, as was to be expected, had virtually no effect against both cockroaches within the test period of 2 hours.
Wurde Transfluthrin mit Flufenoxuron in wasserbasierenden Sprühdosen kombiniert, so ergab sich gegen Deutsche Schaben auf allen geprüften Oberflächen eine deutliche bis erhebliche bessere Wirkung der Kombinationen gegenüber der Transfluthrin-Monosprühdose (Tabelle 11).If transfluthrin was combined with flufenoxuron in water-based spray cans, German cockroaches showed a significantly better to the better effect of the combinations compared to the transfluthrin monospray on all surfaces tested (Table 11).
Auch bei den Orientalischen Schaben wurden in den meisten Fällen durch die Kombinations-Sprühdosen eine deutlich bessere Wirkung erzielt, was besonders auf PVC und lasierte Kacheln zutraf (Tabelle 12).In the case of Oriental cockroaches, too, the combination spray cans achieved a significantly better effect in most cases, which was particularly true for PVC and glazed tiles (Table 12).
Diese Wirkungsverbesserungen werden offensichtlich durch synergistische Effekte des Flufenoxurons hervorgerufen. These improvements in effectiveness are obviously caused by the synergistic effects of flufenoxuron.

Claims

Patentansprüche claims
1. Insektizide und akarizide Wirkstoffkombinationen, welche neben den üblichen Zuschlagstoffen mindestens ein synthetisches Pyrethroid oder natürliches Pyrethrum und mindestens einen Insekten-Entwicklungshemmer enthalten.1. Insecticidal and acaricidal active substance combinations which, in addition to the usual additives, contain at least one synthetic pyrethroid or natural pyrethrum and at least one insect development inhibitor.
2. Insektizide und akarizide Wirkstoffkombinationen gemäß Anspruch 1, dadurch gekennzeichnet, daß sie ein Kurzzeitpyrethroid enthalten, welches als Einzelwirkstoff eine biologische Wirkdauer von weniger als 14 Tagen aufweist, und als Insekten-Entwicklungshemmer einen Chitin- Synthese- hemmer aus der Klasse der Benzoylharastoffe enthalten.2. Insecticidal and acaricidal active substance combinations according to claim 1, characterized in that they contain a short-term pyrethroid, which as a single active substance has a biological duration of action of less than 14 days, and contain a chitin synthesis inhibitor from the class of the benzoyl hara substances as an insect development inhibitor.
3. Insektizide und akarizide Wirkstoffkombinationen gemäß Anspruch 1, dadurch gekennzeichnet, daß sie ein Kurzzeitpyrethroid enthalten, welches als Einzelwirkstoff eine biologische Wirkdauer von weniger als 14 Tagen aufweist, und als Insekten-Entwicklungshemmer einen Chitin-Synthese- hemmer aus der Reihe wie z.B. Lufenuron,3. Insecticidal and acaricidal active substance combinations according to claim 1, characterized in that they contain a short-term pyrethroid, which as a single active substance has a biological duration of action of less than 14 days, and as an insect development inhibitor, a chitin synthesis inhibitor from the series such as e.g. Lufenuron,
RH 5849 (2-Benzoyl-l-(l,l-dimethylethylbenzoesäurehydrazid); Chlor- fluazuron; Diflubenzuron, N-[[[3,5-Dichlor-4-(4-chlorphenoxy)phenyl]- amino]carbonyl]-2,6-difluorbenzamid; Flufenoxuron; Flucycloxuron; Penfluron; Teflubenzuron; Hexaflumuron; Tebufenozide; 2-Chlor-N-[[[4-(l- phenylethoxy)-phenyl]-amino]-carbonyl]-benzamid; Natrium- l,4-bis-(2- ethylhexyl)-sulfobutandioat; Novaluron; 2-Chlor-N-[[[4-(2,2-dichlor- 1, 1- difluorethoxy)-phenyl]-amino]-carbonyl]-benzamid; 6-Azido-N-cyclopropyl- N'-ethyl-l,3,5-triazin-2,4-diamin; N-[[[5-(4-bromphenyl)-6-methyl-2- pyrazinyl]-amino]-carbonyl]-2,6-dichlorobenzamid; 2,6-Dichlor-N-[[(4- chlorophenyl)amino]-carbonyl]-benzamid; Methoprene; Triflumuron;RH 5849 (2-benzoyl-l- (l, l-dimethylethylbenzoic acid hydrazide); chlorofluazuron; diflubenzuron, N - [[[3,5-dichloro-4- (4-chlorophenoxy) phenyl] amino] carbonyl] -2 , 6-difluorobenzamide; flufenoxuron; flucycloxuron; penfluron; teflubenzuron; hexaflumuron; tebufenozide; 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide; sodium 1,4 bis (2-ethylhexyl) sulfobutanedioate; novaluron; 2-chloro-N - [[[4- (2,2-dichloro-1, 1-difluoroethoxy) phenyl] amino] carbonyl] benzamide; 6 -Azido-N-cyclopropyl-N'-ethyl-1,3,5-triazine-2,4-diamine; N - [[[5- (4-bromophenyl) -6-methyl-2-pyrazinyl] amino] -carbonyl] -2,6-dichlorobenzamide; 2,6-dichloro-N - [[(4-chlorophenyl) amino] carbonyl] benzamide; methoprene; triflumuron;
Pyriproxifen; Fenoxycarb enthält.Pyriproxifene; Fenoxycarb contains.
4. Insektizide und akarizide Wirkstoffkombinationen gemäß Anspruch 1, dadurch gekennzeichnet, daß sie Transfluthrin oder natürliches Pyrethrum und als Insekten-Entwicklungshemmer Triflumuron und / oder Flufenoxuron enthalten. 4. Insecticidal and acaricidal active substance combinations according to claim 1, characterized in that they contain transfluthrin or natural pyrethrum and as an insect development inhibitor triflumuron and / or flufenoxuron.
5. Insektizide und akarizide Wirkstoffkombinationen gemäß Anspruch 1, dadurch gekennzeichnet, daß sie 0,01 bis 2.0 Gewichtsprozent Transfluthrin und 0.005 bis 10.0 Gewichtsprozent Triflumuron und/oder Flufenoxuron enthalten.5. Insecticidal and acaricidal active compound combinations according to claim 1, characterized in that they contain 0.01 to 2.0 percent by weight of transfluthrin and 0.005 to 10.0 percent by weight of triflumuron and / or flufenoxuron.
6. Insektizide und akarizide Wirkstoffkombinationen gemäß Anspruch 1, die6. insecticidal and acaricidal active substance combinations according to claim 1, the
0.01 bis 0.2 Gewichtsprozent Transfluthrin und 0.005 bis 1 .5 Gewichtsprozent Triflumuron und/oder Flufenoxuron enthalten.Contain 0.01 to 0.2 percent by weight transfluthrin and 0.005 to 1.5 percent by weight triflumuron and / or flufenoxuron.
7. Wirkstoffkombinationen gemäß der Ansprüche 1 bis 6, dadurch gekenn¬ zeichnet daß es sich um Sprayformulierungen handelt.7. active ingredient combinations according to claims 1 to 6, characterized gekenn¬ characterized in that it is spray formulations.
8. Wirkstoffkombinationen der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es sich um Formulierungen wie ULV-, Heiß- und Kabelnebel, Emulsionskonzentrate (EC), Emulsionskonzentrate auf Wasserbasis (EW) oder wettable Powders (WP) handelt.8. active substance combinations of claims 1 to 6, characterized in that it is formulations such as ULV, hot and cable mist, emulsion concentrates (EC), emulsion concentrates water-based (EW) or wettable powders (WP).
9. Verwendung von Wirkstoffkombinationen gemäß der Ansprüche 1 bis 8 zur Bekämpfung von tierischen Schädlingen, die im Haushalt oder als9. Use of active ingredient combinations according to claims 1 to 8 for combating animal pests, which in the household or as
Hygiene- oder Vorratsschädlinge vorkommen.Hygiene or storage pests occur.
10. Verfahren zur Bekämpfung von tierischen Schädlingen, die im Haushalt oder als Hygiene- oder Vorratsschädlinge vorkommen, dadurch gekennzeichnet, daß man Wirkstoffkombinationen gemäß den Ansprüchen 1 bis 8 auf derartige Insekten bzw. Milben und/oder ihren Lebensraum einwirken läßt. 10. A method for combating animal pests which occur in the household or as hygiene or storage pests, characterized in that active substance combinations according to claims 1 to 8 are allowed to act on such insects or mites and / or their habitat.
PCT/EP1996/003455 1995-08-16 1996-08-05 Active substance combinations comprising pyrethroids and insect-development inhibitors WO1997006687A1 (en)

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MX9801242A MX9801242A (en) 1995-08-16 1996-08-05 Active substance combinations comprising pyrethroids and insect-development inhibitors.
JP9508896A JPH11511152A (en) 1995-08-16 1996-08-05 Combinations of active compounds including pyrethroids and insect development inhibitors
BR9610228-4A BR9610228A (en) 1995-08-16 1996-08-05 Combinations of active pyrethroid compounds and insect development inhibitors
EP96927686A EP0845944B2 (en) 1995-08-16 1996-08-05 Active substance combinations comprising pyrethroids and insect-development inhibitors
DE59606147T DE59606147D1 (en) 1995-08-16 1996-08-05 COMBINATIONS OF ACTIVE SUBSTANCES MADE FROM PYRETHROIDS AND INSECT DEVELOPMENT INHIBITORS
AU67424/96A AU706903B2 (en) 1995-08-16 1996-08-05 Active compound combinations of pyrethroids and insect development inhibitors
US09/011,451 US6270784B1 (en) 1995-08-16 1996-08-05 Active substance combinations comprising pyrethroids and insect development inhibitors
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EP1414304A1 (en) 2001-07-25 2004-05-06 Syngenta Limited Insecticidal mixture containing gamma-cyhalothrin
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US7906127B2 (en) 2001-07-25 2011-03-15 Syngenta Limited Insecticidal mixture containing gamma-cyhalothrin
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WO2003069990A3 (en) * 2002-02-22 2004-04-15 Ishihara Sangyo Kaisha Composition and method for controlling house insect pest
US7344707B2 (en) 2002-05-15 2008-03-18 The Procter & Gamble Company Low combustion aerosol products in plastic packages having a reduced fire hazard classification that subsequently reduces storage costs
WO2005053394A2 (en) * 2003-12-05 2005-06-16 Bayer Cropscience Aktiengesellschaft Synergistic insecticide mixtures
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BR9610228A (en) 2000-03-28
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ES2152550T3 (en) 2001-02-01
GR3035382T3 (en) 2001-05-31
EP0845944A1 (en) 1998-06-10
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